Novel quaternized heterocyclic monoazo dyes

ABSTRACT

The quaternized heterocyclic monoazo dyes having as a diazo component a nitrogen containing cyclic group linked through the azo bridge to an imidazo heterocyclic coupler prepared by quaternization of the intermediate azo dye, are useful as dyes for acyclic, modacrylic and acid-modified polyester textile materials.

United States Patent 1191 Fisher et al. Dec. 23, 1975 NOVEL QUATERNIZED HETEROCYCLIC [58] Field of Search 260/ 146 R, 147, 153, 154, MONOAZO DYES 260/156, 157, 158, 162, 163

[75] Inventors: John G. Fisher; James M. Straley,

both of Kingsport, Tenn. [56] References Cited [73] Assignee: Eastman Kodak Company, UNITED TA PATEN S Rochester, NY. 2,432,419 12/1947 Heimbach 260/154 x 2,569,418 9/1951 Kellog 260/154 [22] 1973 2,790,172 4/1957 Rudner 260/158 ,x [2]] A l N 341,416 3,420,813 l/l969 Mueller et al. 260/156 Related Application Data Primary Examiner-Charles F. Warren [63] Continuation of Ser. No. 661,215, Aug. 17, 1967, abandoned, which is a continuation-in-part of Ser.

Nos. 484,720, Sept. 2, 1965, abandoned, and Ser. ABSTRACT Sept" 1965 abandmed' The quatemized heterocyclic monoazo dyes having as a diazo component a nitrogen containing cyclic group [52] US. Cl. 260/156, 260/153, 260/154, linked through the azo bridge to an imidazo heterocy 260/244 R; 260/248 CS; 260/249.5; 260/251 A; 260/256.4 F; 260/288 R; 260/294.9; 260/296 B; 260/305; 260/306.7; 260/307 FA Int. Cl. C09B 43/00 clic coupler prepared by quaternization of the intermediate azo dye, are useful as dyes for acyclic, modacrylic and acid-modified polyester textile materials.

13 Claims, No Drawings NOVEL QUATERNIZED' HETEROCYCLIC MONOAZO DYES Thisinvention relates to novel monoazo compounds useful as dyes for hydrophobic textile materials such as polyester and cellulose acetate and to novel cationic monoazo compounds useful as dyes for acrylic, modacrylic, and acid-modified polyester textile materials.

The novel compositions of matter have the formula wherein A represents the remainder of a 5 or 6 membered heterocyclic ring system attached to the azo group through a ring carbonatom, the ring atoms of A consisting of carbon or carbon and at least one sulfur 'or nitrogen atom, the non-azo nitrogen ring atom to which A is attached being in' conjugation with the azo group.

R represents lower alkyl or benzyl;

n represents or 1;

R represents a phenyl group;

B represents N or CH;

Z represents the remainder of a heterocyclic ring system which, with the carbon and nitrogen atoms to which Z is attached, completes a 5 or 6 membered ring, the ring atoms of Z consisting of carbon or carbon and at least one nitrogen, sulfur or oxygen atom; and

X represents an anion. x

The unquatemized compounds of the invention, i.e., when n is 0, dye hydrophobic textile materials such as polyester, cellulose acetate, and polyamide fibers in a broad range of shades. The cations of the invention, i.e., when n is l, have excellent affinity for acrylic, modacrylic, and acid-modified textile materials, and, when applied thereto by conventional means, display excellent properties such as, for example, fastness to light and wet processing.

Examples of the diazo components from which the unsaturated residue represented by A is derived include the thiazoles and benzothiazoles, i.e. A represents the pyrazoles, i.e. A represents the l,3,4-thiadiazoles,'i.e. A represents l J-SC=N.

the isothiazoles, i.e. A represents the pyridines and quinolines, i.e. A represents shite;

the 2-benzimidazoles, i.e. A represents The carbon atoms of the diazo component, i.e. the groups collectively represented by A and N in formula (I) except, of course the carbon atom attached to the azo groups, can be substituted with various substituents including a fused carbocyclic ring which may also be substituted. Examples of such substituents are hydrogen, lower alkyl, lower alkoxy, lower alkanoylamino, aroylamino, nitro, halogen, cyano, lower alkylsulfonyl, arylsulfonyl, carbamoyl, lower alkylcarbamoyl, di-

' lower alkylcarbamoyl, benzamido," lower alkoxycarbonyl, hydroxy, lower alkanoyl, aroyl, lower alkylsulfonamido, sulfamoyl, lower alkylsulfamoyl, di-lower alkylsulfamoyl, thiocyanato, alkythio, aryl, aryloxy, etc. As used herein, the work lower denotes an alkyl moiety having up to about 4 carbon atoms.

Examples of the alkyl and alkoxy groups that can be present onthe diazocomponent includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, methoxy,ethoxy, propoxy, and substituted alkyl such as cyanoalkyl, e.g. 2-cyanoethyl, haloalkyl, e.g. 2-chloroethyl, 3-bromopropyl, trifluoromethyl, nitroalkyl, e.g. 2-nitroethyl, hydroxyalkyl, Z-hydroxyethyl, 2,3-dihydroxypropyl, etc. Bromine and chlorine are representative of the halogen atoms. Acetyl, propionyl, butyryl, acetamido, propionimido, and butyramido are representative of the alkanoyl and alkanoylamino groups that can be present on the diazo component.

Typical alkylsulfonyl and alkylsulfonamido groups that can be present on the diazo component of the compounds and cations of the invention are methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2- cyanoethylsulfonyl, methylsulfonamido, ethylsulfonamido, butylsulfonamides, etc. Examples of the alkoxycarbonyl groups include methoxycarbonyl, e'thoxycarbonyl, propoxycarbonyl, butoxycarbonyl, etc. Typical of the alkyl groups of the alkylthio or substituted carbamoyl or substituted sulfamoyl groups that of the groups represented by thedivalent chain Zinclude the following groups.

a 45 g g R 3 can be present on the diazo component are methyl, ethyl, propyl, isopropyl, butyl, etc.

Examples of the aryl groups that can be present on the diazo compound include monocyclic, carbocyclic aryl such as phenyl and phenyl substituted with lower alkyl, lower alkoxy, halogen, nitro, cyano, etc. The aryl moiety of the aroyl, aroylamino and arylsulfonyl groups can be unsubstituted, e.g. benzoyl, benzamido, phenylsulfonyl, or substituted with the groups mentioned above in the definition of aryl. I

Any secondary nitrogen atoms present in the group represented by A can be unsubstituted or substituted with lower alkyl, lower alkylsulfonyl, aryl, or aroylamino as those groups are defined above. Examples of diazo groups containing a secondary nitrogen are the pyrazoles, the benzimidazoles, and the triazoles'.

The examples and types of substituents described above are illustrative and not limitative. Various substituents that can be present on the diazo component will be apparent to those skilled in the art.

Examples of the alkyl groups represented by R include methyl, ethyl, propyl, isopropyl, butyl and phenylalkyl groups such as'benzyl. Preferably R is methyl or ethyl.

The phenyl groups represented by R can be unsubstituted or substituted with lower alkyl, lower alkoxy. halogen, nitro, cyano, etc. Specific examples of such phenyl groups include, but are not limited to, phenyl, p-tolyl, m-ethyl-phenyl, p-anisyl, p-chlorophenyl, obromo-p-tolyl, o,p-dichlorophenyl, p-nitrophenyl, and

. p-cyanophenyl.

carbon atoms of the unsaturated, divalent groups similar to the carbon atoms of the diazo component.

Examples of the ring atoms'that Z can represent inwherein R represents hydrogen or one or more substituents described above including those substituents that can be present on the carbon atoms of the group represented by A. Preferably, R represents not more than two substituents selected from the-group consisting of alkyl and phenyl groups.

A particularly preferred group of the compounds of 5 the invention are those containing an azole diazo component having'the formula:

cyano, or lower alkyl- 1 i l QZ l J wherein R represents methyl or ethyl; R represents hydrogen, thiocyanato, lower alkyl, or lower alkylsulfonyl; I. R represents hydrogen, lower alkyl, phenyl, or phenyl substituted with loweralkyl, lower alkoxy,

or halogen; and .i R represents hydrogen, loweralkyl, lower alkoxy or halogen.

A preferred group of the coupler components of the novel compounds of the invention have the formula:

rhr i Y I or' l (II) v p I N/ A-NH v and coupling the resulting diazonium salt with a compound having the formula II) R2 1 Y L I wherein A, R and Z are defined above. The amines of formula (II): and the coupling procedures that can be used are well known in the art of dye chemistry. I The couplers of formula (III) are 'prepar'e'dby methods, or methods analagous to those, described in the literature. The reaction by which the couplers are prepared isillustrated by the following equation: I

thiazole, 2-amino-6-trifluoromethylbenzothiazole, 2- amino-5-methyl-6-acetylbenzothiazole, 2-amino-6- ethoxycarbonylbenzothiazole, 2-amino-6- acetamidobenzothiazole, 2-amino-6-thiocyanato-benzothiazole, Z-amino-o-carbamoylbenzothiazole, 2- amino-S-methylthio- 1 ,3 ,4-thiadiazole, amino-5-(ethoxycarbonylmethylthio)- l ,3,4- thiadiazole, 2-amino--methylsulfonyl-1 ,3,4-thiadiazole, 3-'amino'-l,2,4-triazole, 2-aminobenzimidazole, 2- amino-S-methylbenzimidazole, .2-amino-6- methylsulfonylbenzimidazole, 2-amino-6-chlorobenzimidazole, 3-aminoisothiazole, 3-amino 5-nitroisothiazole, 3-amino-4,5-dimethylisothiazole, 3-amino-5 cyanoisothiazole, 3-amino-5-methylsulfonylisothiazole, 3-aminopyrazole, 3 -amino-4-cyanopyrazole, 3-amino- 4-nitropyrazole, 3 -amino-4-ethylpyrazole, 3-amino-4- ethoxycarbonylpyrazole, Z-aminopyridine, 4- aminopyridine and 4-aminoquinoline. ln general, any amino-cyclic compound which can be diazotized, and conforms with the definition of the diazo component in formula (1), can be used 'to prepare the novel'compounds of the invention. a

The novel cationic compounds of the invention are prepared by treating the monoazo compounds described above with an alk ylat'ing agent at elevated temperature with or without an inert solvent. Suitablealkylat'ing agents that can be used are the dialkyl sulfates, the alkyl halides, the aralkyl halides, the alkyl esters of 0 0 WELT-[Br H t u R -T, H N-E RC CHE-X I Nd \L NaOAc aryl sulfonic acids, etc; Examples of such alkylating agents include dimethyl sulfate, diethyl sulfate, dipropyl sulfate, ethyl bromide, butyl bromide, methyl iodide, ethyl iodide, benzyl chloride, benzyl bromide, methyl-p-toluene sulfonate, butyl-p-toluene sulfonate, and ethyl benzenesulfonate.

Examples of the anions represented by X include Cl, Br, 1, CH SO C H SO etc., the anion depending upon the method of isolation utilized and the particular quaternizing agent employed. The anion does notiaffect the utility of the cations of the invention as dyes nor does it affect the dye affinity of the cations for polyacrylonitrile textile materials. When the compounds are used to dye polyacrylonitrile textile material, the anion becomes associated with a positively charged ion derived from the polyacrylonitrile and is removed from the dye cation and polyacrylonitrile textile material, either in th *"bsequent washing of the dyed polyacrylonitrile textile material. Since the cation of a cationic azo dye is responsible for the color of the compound and the particular anion associated with the cation is not important, the cations of the novel cationic compounds of the inven tion are described in the Examples herein without being associated with any anion.

As is well known in the art of dye chemistry. the primary color of the compounds of the invention is attributable to the conjugation of the compounds and cations as shown in formula (I). For this reason, the groups represented by A, R B and Z, as these groups are defined herein, are not important with respect to the usefulness of the compounds as dyes for the described textile materials. The groups represented by A, R B and Z and the substituents, if any, that are present on these groups function primarily as auxochrome groups to vary the color of the compounds and cations.

The unquaternized and quaternized compounds of the invention and their preparation are further illustrated by the following examples.

PREPARATION OF THE COUPLERS EXAMPLE 1 6,6-Dimethyl-8-keto-2-phenyl-5,6,7,8-tetrahydroimidazo[ 2, l -b]-benzothiazole 12.5 g. of product melting at 175l78C. and having the structure:

EXAMPLE 2 2-Phenylimidazo[ l,2-a]pyrimidine An equimolar mixture of 2-aminopyrimidine and a-bromoacetophenone are heated in absolute ethanol for several hours at 60-70C. Anhydrous ether is added to precipitate the hydrobromide of the product. The free base, melting at 202C, is obtained by the action of aqueous Na CO solution and has the forv A 8 EXAMPLE 3 7-Methyl-2-phenylimidazo[ l ,2-c lpyrimidine Substitution of 4amino-6-methylpryimidine yields a coupler which melts at 244 C. and has the structure:

EXAMPLE 4 2-Phenylimidazo[2, l -b]benzothiaz0le A 0.2 m. quantity each of 2-aminobenzo thiazole and a-bromoacetophenone are mixed in 350 ml. of chloroform and heated at refluxfor 1 /2 hours. After cooling,

the solid intermediate product is filtered off and slur-' -ried in 2 1. water containing 10ml. of 48% hydrobromic acid. This is then heated to a boil, filtered hot, and afler allowing to cool the filtrate is basified with NH OH to yield 6.8 g. of 2-phenylimidazo[2,l-b]benzothiazole melting at 108-10 having the formula:

EXAMPLE 5 2-Phenylimidazol l,2-a]pyridine 0.1 m. Quantities of 2-aminopyridine and abromoacetophenone are heated in ml. of chloroform at reflux for 2 hours. The chloroform is evaporated and the oily residue taken up in 10% HCl, warmed, charcoal added and filtered. The filtrate is neutralized with NH OH and the solid product isolated and recrystallized from ethanol. The yield of product is 12.7 g., melts at l35-l 37C. and has the structure:

EXAMPLE 6 2-iPhenyl-5 ,6,7,8-tetrahydroimidazol 2, l -b]benzothiazole 10.1 g. of 2-amino-l,3,4-thiadiazole is dissolved in 160 ml. of ethanol; 19.9 g. of a-bromoacetophenone is 5 added and the solution is heated and stirred at reflux for 1 hour. After cooling, the solid is filtered off and dissolved in 750 ml. of water and 40 ml. of 48% hydrobromic acid. This solution is heated at reflux for 1 hour, neutralized by addition of solid ammonium acetate and refluxed V2 hour longer. After cooling, the product is collected on a filter, washed with water and dried. The yield of product is 13 g. melting at l27-l30C. It has the formula:

EXAMPLE 8 6-Phenylimidazo[2, lblthiazole Bromine (21.5 ml.) is added to a solution of 50 g. of acetophenone and 0.1 g. of anhydrous AlCl in 200 ml. of chlorobenzene. The addition requires about 20 minutes and the temperature of the reaction solution rises to about 35C. Dry air is bubbled through the solution until all the gaseous HBr is removed. Z-Aminothiazole (24 g.) is added and the reaction mixture stirred and heated on a steam bath for 1 hour. The thick reaction mixture is filtered while still hot and the filter cake washed with hexane. The dry product is slurried in 200 ml. of methanol and then diluted with a solution of 80 g. ammonium acetate in 1600 ml. of water. This suspension is stirred and heated to 80C., then filtered and the product thus obtained is washed with 4 l. of water. The yield is 70 g. of product which melts at l43l44C. and has -the structure:

gous to those described in the preceding examples. For example, the compound having the structure:

is prepared as described in Ben, 60,1607 (1927) and the compound having the formula:

is prepared as described in :Pharm. Soc. Japan, 1050 (1937); CA, 32, 33985.

. E19. PREPARATION oF THE MONOAZO coM ouNos I EXAMPLES 0.72 g. of NaNO are added to 5 ml. of H 80 keeping the temperature below 70C 10 ml. of l-5 acid are added to the nitrosyl sulfuric acid below 20C., then with further cooling at to C. 1.47 gfof 2-amino-5- methylthio-l,3,4-thiadiazole are added. A second portion of ml. of l5 acid is added below 5C. and the diazotization is completed by stirring for two hours at 3 to 5C. Thisdiazo solution is then added to a fine suspension of the hydrochloride of the coupler prepared as follows: 2.0 g. of 6-phenylimidazo[2,l-b]- thiazole is dissolved by heating in 400 ml. of water containing 5 ml. of cone. HCl, ice is then added which precipitates the hydrochloride salt of the coupler in fine suspension. The coupling mixture is buffered to a pH of 4 to- 5 by addition of solid ammonium acetate. After intermittant stirring for two hours, the productis collected on a funnel, washed well with water, anddried at room temperature. This compound imparts fast orange shades to cellulose acetate and polyester fibers. It has the following structure:

EXAMPLE l0 When the 2-amino -5-methylthio l,3,4-thiadiazole of Example 9 is replaced with 1.61 g. of 2-amino-5- ethylthio-1,3,4-thiadia2ole and the procedure of Example 9 is duplicated, a dye is obtained which dyes cellulose acetate and polyester fibers in fast orange shades. It has the structure:

EXAMPLE 1 l The procedure described in Example 9 is repeated using 2.l9 g. of Z-amino-5-ethoxycarbonylmethylthio- 1,3,4-thiadiazole in place of the thiadiazole used in that Example. The product obtained imparts orange shades to polyester and cellulose acetate fibers and has the formula:

EXAMPLE 12 According to the procedure described in Example 9, 1.79 g. of 2-amino-5-methylsulfonyl-l,3,4-thiadiozole is diazotized and coupled with 2.0 g. of 6- phenylimidazolZ,l-b]thiazole. The product obtained gives reddish-orange dyeings on polyester fibers and has the formula:

l ll l 1 jg o N- l l ch ..0 k N The azo compounds described in the Examples of Table lare prepared according to the procedure described in Example 9 by diazotizing the appropriate compound of formula (II) and coupling it with the appropirate coupler having formula (III). The coupounds conform to the general formula:

2 R l%J N=N l \J TABLE Example No R6 R B 13 CH3$- Q N H 01 Q N 15 04 5- N 18 C2H5SO2- Q N 19 H Q CH 20 H Q, CH 21 H Q CH EXAMPLE 22 2-amino-5-nitrothiazole (1.45 g.) is dissolved in 6.8 ml. of conc. H SO and 12.5 ml. of water at about room temperature. This solution is treated with a solution of nitrosyl sulfuric acid containing 0.76 g. of NaNO below -5C. The diazotization is complete after l5 minutes at 5 to -l0C. This solution is added to a suspension of 2.0 g. of the hydrochloride of 6- phenylimidazo[2,l-blthiazole and coupling is carried out as described in Example 9. The compound obtained imparts pink shades to cellulose acetate and polyester fibers and has the structure:

KL... jaw i] EXAMPLE 23 The procedure described in Example 22 is repeated using 2.2 g. of 2-amino-5-N-butyl-sulfonylthiazole in place of the 2amino-5-nitrothiazole. The compound thus obtained imparts a fast orange shade to polyester fibers and has the formula:

Color or Polyester Fibers orange Orange orange yellow goldenyellow l reddish orange /S l yellowish orange 11 I orange yellow EXAMPLE 24 10 ml. of l5 acid [propionic to acetic] are added below 20C. to a solution of nitrosyl sulfuric acid prepared from 0.72 g. of NaNO and 5 ml. of concentrated H l g. of 2-aminothiazole is then added keeping the temperature below 5C., followed by a second 10 EXAMPLE 25 I I 1 1.0 g. of Z-aminothiazole is diazotized as described in, I R2 3 Example 24. It is coupled to l g of 6- 15 4 y l r l phenylimidazo[2,1-b]-1,3,4-thiadizole, prepared as v s N=N TABLE 4 Q Color on EXAMPLE NO, R L z Polyester Fiber a /S 26 H N orange 27 H N olden yellow v I /5 28 4-CH 3 N allium-yellow j 29 4Q N '2 l crange '30 4 N l orange i /S] 4- I 3 N I I CH3 grunge 32 5-SCN-4 I N Y red-orange 33 S-SCN-4-- N IN orange /S 34 5-SCN-4---: N I CH3 red-orange 35 S-SCN-4 N I red-orange /S 36 l"a--SCN-- CH N orange 37 5--NO2 N I pink 7 3B 5'-Br N orange 5 39 S-Bl' N orange 4O 5-SO C H -n Q N orange 41 5.50 04 N Orange described above, in 30ml; of 1 5 acid cooled in an ice bath. The mineral acid is neutralized with NH OAc keeping to the temperature. below 10C. The coupling is completed by intermittent stirring for 2 hours without furthercooling.

The compounds" described in Table ll are prepared by diazotizing the appropriate aminothiazole and coupling it with the appropriate coupler compound of formula (lll) according to the procedure described in Examples 22 and 24. The compounds conform to the following fonnula:

TABLE ll (conlinund) Color on Pol esler Fiber EXAMPL E NO yellow @QQQQQQQ yellow yell ow Y llow yellow yellow Y ll w yellow yell ow yellow yell ow yall ow orange yellow yellow yell ow yellow yellow eddish-yell ow yellow H H N N N N N N N N N m c c 3 H 3 3 m m O C 3 3 3 H H H H H C J JL H H H H H H H 4 4 5 0 I 2 3 4 S 6 7 8 9 0 l 5 s 5 s 5 5 5 s 5 5 6 6 EXAMPLE 62 1.50 g. of 2-aminohenzothiazole is dissolved in 24 ml. of water and 14 ml. of H 50 The solution is cooled to C. and a solution of .72 g. of NaNO in ml. of H 80. is added at 0 to 5C. The diazotization is completed by stirring at 3 to 5C. for two hours. It is added to a finely divided suspension of the hydrochloride of 6- phenylimidazo-[2,l-b]thiazole prepared as follows: 2.0 g. of 6-phenylimidazo-l2, l-blthiazole is dissolved by heating in 400 ml. of H 0 and 5 ml. of cone. HCl, ice is added which precipitates the hydrochloride as a fine suspension. The coupling mixture is treated with solid ammonium acetate to bring the pH to about 4.5. After intermittent stirring for two hours the product is collected, washed well with water and dried. It imparts orange shades to cellulose acetate and polyester fibers and has the structure:

EXAMPLE 64 2-amino-6-methylsulfonylbenzothiazole (2.28 g.) is dissolved in 50 g. of 50% H 80 A solution of 0.72 g. of NaNO in 5 ml. of cone. H 80 is added to this solution keeping the temperature below 5C. The diazotization is completed by stirring for two hours at 35C.

I This diazo solution is added to a suspension of the EXAMPLE NO. R

7 s-cu so 68 6-CH3SO2 s9 6..CH so 7o 6-CH3502 H 6-CH s0 hydrochloride of 2.0 g. of 6-phenylimidiazo-[2J- b]thiazole prepared as described in Example 62. and the coupling carried out as therein described. The product obtained imparts fast orange shades to cellulose acetate and polyester fibers.

EXAMPLE A solution of nitrosyl sulfuric acid prepared from 0.72 g. of NaNO and 5 ml. of H 50 is treated with l0 ml. of 1:5 acid (1 part propionic acid:5 parts acetic acid) below 20C., then 1.75 g. of 2-amino6- cyanobenzothiazole is added keeping the temperature below 5C. A second portion of 10 ml. of [:5 acid is added at 35C. and the diazotization completed by stirring two hours at this temperature. This diazonium sulfate solution is reacted with 2.0 g. of 6- phenylimidazo-l2,l-b]thiazole as described in Example 62. The resulting azo dye imparts fast orange shades to cellulose acetate and polyester fibers.

EXAMPLE 66 0.72 g. of NaNO is dissolved in 5 ml. of concentrated H allowing the temperature to rise to about 65C. 10 ml. of l-5 acid is added below 20C. followed by 1.8 g. of 2-amino-6-methoxybenzothiazole at 0 to 5C. Then a second 10 ml. portion of l-5 acid is added below 5C. The diazotization is completed by stirring at 3 to 5C. for 2 hours. The diazo solution is added to a cooled solution of L94 g. of 2-phenylimidazo[l,2-a]- pyridine in 25 ml. of l-5 acid. The mineral acid is neutralized by addition of solid ammonium acetate keeping the temperature below 10C. After 2 hours the coupling mixture is drowned in 600 ml. of water and the product is filtered and washed well with water. This azo compound imparts a red-orange shade to polyester fibers.

The compounds described in Table III are prepared by reacting the appropriate aminobenzothiazole with the appropriate coupler. The azo compounds conform to the formula:

TABLE 111 Color on 2 Polyester L l rib."

N orange 5 N Orange S N I Yellow O S N CH Orange N orongc TABLE Color on Ill (continued) ol ester Fibor EXAMFl. E NO.

orange orange orange 95 o-cn coorange 96 6--CH SO yellow yallowishorange yullowishorongq yellowi shorange yellowish-orange lOl yellowish-orange yellow yellow yellow orange orange N N N N N a 3 w s m m l i C H d C 6 6 6 6 6 4 2 3 4 O O O 5 6 7 I I I 0 O O I I I Yellow yellowish orange yellowish orange Ill Y llowish orange yellow @QQQQQQ TABLE III (ccnlinued) Co'or on Polyester 8 Z Fibers EXAMPLE 1 l5 3-Amino- 1(H). 1.2.4-triazole (0.84 g.) is dissolved in f acetic acid (10 ml.) and cone. HCI (3ml.). This solu- 10 L N tion is cooled to C. and treated with a solution of NaNO; (0.72 g.) in water keeping the temperature below 5C. After the diazotization is complete, the

solution is added to an ice cooled solution of 6- phenylimidazo (2,l-b) hizllole in acid m The compounds of the Examples set forth in Table IV The coupling mixture is neutralized to congo brown by are prepared by diazotizing the appropriate aminoaddition of solid NH OAc keeping the temperature trizole and coupling the resulting diazonium salt with below C. After completiOn o p g Show" y the appropriate coupler. The compounds have the gen- 21 negative Rsalt test) water is added and the yellow f l solid collected, washed with water and air dried to yield 2 I I w N=N l- J EXAMPLE NO. R

2.6g. The product has the formula:

g st i EXAMPLE ll6 The triazolylazo compounds can be used for dyeing According to the procedure described in Example polyester and cellulose acetate fibers. However, such 1 15, 3-amm0-l(H) 1,2,4-triazole (0.84 g.) is diazouse of the compounds is of secondary importance, the tlYSd and coupled with 2-phenylim1dazo (2,1-b) benzoprimary use of the triazolylazo compounds being prethlazole. The 2120 compound obtained has the struccursors for the quanternized triazolylazo cations deture: scribed hereinafter.

TABLE IV EXAMPlE NO. R2 B 5 I20 N N s o CH 3 124 Q N c14 s l2 7 CH l CH 3 By using procedures analagous to those described hereinabove, additional compounds can be prepared. In Table V, the diazotizable amine corresponds to formula (II) and the coupler corresponds to formula (III).

TABLE V Ex. No. DIAZOTIZABLE AMINE COUPLER I28 3-amino-4-cyanopyrazole fi-phenylimidazol 2.l -h I thiazole I29 3 -aminopyrazole Z-phenylimidazol 2. I -b] benzothiazole I30 3-aminopyrazole 6.6-dimethyl-8-kcto- 2-phenyl-5,6,7,8- tetrahydroimidazol 2. l -h] benzothiazole l 3 I 3-amino-4-nitropyrazole o-phenylimidazol 2, l -b thiazole I32 3-amino-4-bromopyrazole 3-methyl-6-phenylimidazo [2,l-blthiazole I33 3-amino-4-ethoxycarbonyl- Z-phenylimidazol l.2-a]- pyrazole pyrimidine I34 3-aminoisothiazole o-phenylimidazol 2, l -b]- thiazole 1 I35 3-amino-5-nitroiso- Z-phcnylimidazol l,2-a]- thiazole pyridine I36 4-aminopyridine 6-phenylimidazol 2, l b

'thiazole I37 4'aminoquinoline 3-phenyl-6-phenylimidazo [2,l-blthiazole I38 Z-aminobenzimidazole 6-phcnylimidazo[ 2, l -h thiazole I39 2-amino-6-mcthoxy- 3-methyl-6-phenylimidazo benzimidazole [2,lb|thiazole I40 2-amino-t'a-mcthylsulfonylfi-phenylimidazol 2, I -b henzimidazolc thiazole PREPARATION OF THE AZO CATIONS EXAMPLE 141 EXAMPLE 142 0.5 g. of the dye of Example 25is quaternized as I described in Example 141 except the period of heating in dimethyl sulfate is extended to 1 hour. The cation obtained dyes acrylic fibers in fast yellowish-red shades and has the structure:

, ,3 E) N gr Y we EXAMPLE I43 1.0 g. of the azo dye described in Example 42 is dissolved in 40 ml. of chlorobenzcne at the boil. The solution is filtered into a flask containing 1 ml. of dimethylsulfate and heated and stirred on the steam bath for 1.25 hours. Afterallowing to cool the solid is filtered off and-washed with hexane. For purification the product is recrystallized from alcohol. This cation dyes acrylic fibers in fast red shades and has the structure:

EXAMPLE I44 and has the structure:

Gil-I I j- N=N E S EXAMPLE 145 0.5 g. of the compound described in Example 45 is heated in 10 ml. of dimethylsulfate at -100C. for 2 hours. The brownish-red solution is drowned in ether and the precipitated dye is collected on a funnel, washed with ether and dried in a vacuum desiccator. This cation imparts red shades to acrylic fibers and has the structure:

EXAMPLE 146 l g. of the compound of Example 47 is heated in 10 ml. of dimethylsulfate for 2%. hours. The resulting orange solution is drowned inethe r, the ether decanted from the sticky product and the latter dissolved in water by heating. After addition of a small amount of charcoal the hot solution is filtered and the dye is precipitated as the quaternary iodide by addition of potassium iodide. This cation imparts orange shades to acrylic fibers.

The thiazolylazo compounds set forth in Table VI that are described-in Table II are quaternized according to the procedures described in Examples 141 through 146. The cations obtained give fast dyeings on acrylic, modacylic and acidmodified polyester fibers. The color given for each of the following compounds refers to dyeings of the resulting cation on acrylic fibers.

TABLE VI TABLE Vllcontinued- Compound of: Color Compound ofz Color Compound of: Color 7 Compound of: Color Example 43 red Example 2) bluish-red I Example 89 l bluish-red 7 Example 44 orange Example 30 red Example I02 'red Example 9] bluish-red Example 45 red Example 3| bluish-red Example 76 reddish-blue Example 92 bluish-red Example 46 red Example 36 violet Example 78 reddish-blue Exanlple I07 bluish-red Example 47 orange Example 35 violet Example 75 reddish-blue Example 95 hluishrcd Example 48 orange Example 39 violet Example 86 violet Example [08 violet Example 4) orange Example 54 red-violet Example I03 violet Example 83 bluish-red Example 27 red Example 55 red Example 104 violet Example 109 bluish-red Example 50 reddish-violet Example 56 red 1() Example l()5 violet Example l l() bluish-red Example 5l reddish-violet Example 57 red Compound of: Color Example 28 bluish-red Example 58 bluish-red lEmmph; 1 Muishred Example 50 bluish-red Example 59 red Example rcdwiolm Example 53 orange Example 60 bluish-red Example 13 Muishdwd Example l l4 bluishred EXAMPLE 147 Y EXAMPLE 149 0.5 g. of the compound of Example 62 ls quaternlzed l byheating in 5 ml. of methyl-p-toluene sulfonate at 95 T y (1.0 g.) f Example 115 ls dissolved in dry toil00C. for l hour. The violet solution is poured into 20 dlmethylformamlde 4 and treated With m hyl 100 ml. o'f'hexane, stirred well and the hexane de- Sulfate fiat flg at 52- 09 0 0 canted from the precipitated dye. After rinsingtwith mhe y llowi h orange solutlon IS drowned into hexane the dye is purified by dissolving in 300 ml. of Water I00 cohtilmmg Nllcl g-) and Zncl2 hot water and filtering. The cooled filtrate is treated g-)- The Preclplmte which forms is filterfid with NaCl and ZnClto precipitate the product. This ashed with avery small amount of water and air dried. cation imparts fast bluish-red shades to acrylic fibers. It This Cation p t a yellow shades to acrylic and has the formula: modacrylic fibers and has the structure:

l 3 N ll: l l

EXAMPLE I48 The cations resulting from the quaternization of the 0.5 of the compound of Example 66 is quatcrnized 4t) COUPOLmdS described in xample lit; and .Table ,IV with dimethyl sulfate according to the procedure degl e excellent dyelngs on acryl c-type textile fibers, If scribed in Example 141. The quaternary iodide comthe secondary nltrogen atom of the trlazole compopound is recrystallized from ml. of alcohol. The h e number 4 n gn, Ofthe azo compound cation obtained imparts fast violet shades to acrylic 18 n bstituted. the nitrogen atom ls also alkylated fibers and has the f ula; 45 during the quaternlzatlon reaction. The Table Vlll illustrates the cations obtained from ,the, compounds described in Example 116 and Table IV. The color refers to dyeings on acrylic fibers.

TABLE Vlll 3 so Compound of: Color Compound oi: Color Example l|6 reddish-yellow. Example I22 ellow CH3O L =N Example 117 yellow Example 123 yellow S Example 1 l8 yellow Example 124 yellow A Example ll9 yellow Example 125 orange Example I20 yellow Example 126 yellow F.- l-lzl ll E; 2 The cations obtalned by quatermzmg the benzo Ye Xlmpkl 7 thiazolylazo compounds of Examples 59-61 and Table III according to the procedure described in the above I Examples give dyeings of excellent fastness properties on acrylic-type textile materials. The compounds of X M LE 150 Table Vll are quaternized to yield cat ons which glve Th compound of Example 128 (1 g'.) is heated in dyeings on acrylic fibers having the Color ShO ndimethyl sulfate (8 ml.) at 100C. for one hour. TABLE V" The reaction mixture is then drowned in ether and the v ether decanted from the precipitate. The product is Compound 65 dissolved in water and precipitated by the addition of Example 98 hluish red Examp:e 1)316 regwiolet sodium chloride and zinc chloride/This cation'imparts E l 99 bluish-red .xampc re -vloct I y :323 rcdwinlc' Example 64 red. yellow shades to acrylic fibers and has the structure. Example lOl red-violet Example 88 bluish-red v I 1 The monoazo compounds referred to in Table IX are quaternized by employing the above-described procedures. The color given is the color which the resulting cation imparts to acrylic fibers.

TABLE 1X Compound of: Color Compound of: Color Example 129 yellow Example 133 reddishyellow Example I30 yellow Example 134 red Example l3l reddish-yellow Example 135 bluish-red Example 132 yellow Example I36 red Example I37 bluish-red Example 139 bluish-red red Example 140 bluish-red Example 1 38 EXAMPLE 151 The azo compound of Example 9 1.0 g.) is heated in 5 ml. of dimethyl sulfate at 95l00C. for /2 hour. The solution is drowned in ether and the precipitate is filtered off, dissolved in water and reprecipitated after filtering by the a ddition of sodium chloride. The cation obtained imparts fast red shades to acrylic fibers and has the formula:

The compounds set forth below are quaternized according to the procedure of the preceding example. The color given refers to the shade of acrylic fibers dyed with the resultingcation.

Compound of: Color Compound of: Color Example l0 red Example l6 reddish-orange Example ll red Example 17 red Example 12 bluish-red Example 18 bluish-red Example 13 rcddishorange Example 19 red Example 14 red Example 20 red Example 15 red Example 2| reddish-orange EXAMPLE 152 An amount of 0.1 g. of the dye is dissolved in the dye pot by warming in 5 cc. of 2-methoxy ethanol. About 3-5 cc. of a 3% sodium lignin sulfonate aqueous solution is added, with stirring, until a fine emulsion is obtained. Water is then slowly added to a total volume of 300 cc. Then, 3 cc. of an emulsifiable nonionic, modified biphenyl derivative carrier (Carolid: Tanatex Chemical Corp.) are added and 10 grams of a textile fabric made of poly(ethylene terephthalate) fibers are entered. The fabric is worked 10 minutes without heat and then for 10 minutes at C. The dye bath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is. rinsed with water and dried.

When the compounds of this invention are used to dye polyamide textile materials, the above procedure can be employed except the Carolid dyeing assistant need not be used. When cellulose acetate fibers are dyed with the compounds, the above procedure can be followed omitting the Carolid dyeing assistant andcarrying out the dyeing at 80C. for one hour rather than at the boil.

The compounds of the invention can also be applied to polyester textile materials by the heat fixation technique of dyeing. This procedure is described'in U.S. Pat. No. 2,663,612 and in the American Dyestuff Reporter, 42, l (1953).

Polymeric linear polyester materials of the terephthalate type are illustrative of the linear aromatic polyester textile materials that can be dyed with the compounds of our invention. Examples of linear polyester textile materials that can be dyed with the compounds of the invention are those prepared from ethylene glycol and dimethylterephthalate or from cyclohexanedimethanol and dimethylterephthalate. Polyesters prepared from cyclohexanedimethanol and dimethylterephthalate are more particularly described in U.S. Pat. No. 2,901,466. Poly(ethylene terephthalate) polyester fibers are described, for example, in US. Pat. No. 2,465,319. The polymericlinear polyester materials disclosed in U.S. Pat. Nos. 2,945,010, 2,957,745, and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200C. and are sold under the trade names Kodel", Dacron, and Terylene.

Examples of the polyamide fibers that can be dyed with the compounds of the invention are those consisting of Nylon 66, made by the polymerization of adipic ,acid and hexamethylenediamine, Nylon 6, prepared from epsilon-aminocaproic acid lactam, and Nylon 8. The cellulose acetate fibers that can be dyed with the compounds of the invention include fibers consisting of either cellulose triacetate or partially hydrolyzed cellulose acetate.

The cationic monoazo compounds of the invention can be used for dyeing acrylic and modacrylic polymer fibers, yarns and fabrics a broad range of shades. Acrylic textile materials are those which consist of at least acrylonitrile and modacrylic textile materials are those consisting of at least 35% but less than 85% acrylonitrile. The cationic compounds of the invention also give excellent dyeings on acid-modified acrylic textile materials such as the sulfonate modified acrylic fibers described in U.S. Pat. Nos. 2,837,500, 2,837,501 and 3,043,81 l. The novel cationic compounds can also be used to dye sulfonate modified polyester fibers such as are described in U.S. Pat. No. 3,018,272. Examples compounds of the invention are those sold under the trade names Orlon, Orlon 42, Verel, Acrilan, Dynel, Creslan, and Dacron64". In general, the cationic compounds, when used as dyes on the described textile materials, exhibit improved fastness, for example, to washing, to alkaline perspiration, gas (atmospheric fumes) and sublimation.

Textile materials dyed by the cationic compounds of the invention are characterized by containing at least about 35% combined acrylonitrile units and up to about 95% acrylonitrile units, and modified, for example, by 655% of vinyl pyridine units as described in U.S. Pat. Nos. 2,990,393 (Re. 25,533) and 3,014,008 (Re. 25,539) or modified by 655% of vinylpyrrolidone units, for example, as described by U.S. Pat. No. 2,970,783, or modified with 65-5% acrylic ester or acrylamide units as described in U.S. Pat. Nos. 2,879,253, 2,879,254 and 2,838,470. Similar amounts of the other polymeric modifiers mentioned above are also useful. A preferred group of the copolymers readily dyeable with the dyes of the invention are the modacrylic polymers such as described in U.S. Pat. No. 2,831,826 composed of a mixture of (A) 7095% by weight of a copolymer of from 30 to 65% by weight of vinylidene chloride or vinyl chloride and 7035% by weight of acrylonitrile, and (B) 30- by weight of a second polymer from the group consisting of l homopolymers of acrylamidic monomers of the formula wherein R is selected from the group consising of hydrogen and methyl, and R and R are selected from the group consisting of hydrogen and alkyl groups of l6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) copolymers consisting of at least 50% by weight of at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.

Another type of modacrylic polymer that can be dyed with the cationic compounds of the invention is an acetone soluble mixture of (A) 7095% by weight of a copolymer of 30-65% by weight of vinylidene chloride and 7035% by weight of acrylonitrile and (b) 305% by weight of an acrylamide homopolymer having the above formula wherein R and R and R are as described above. Specific polymers of that type contain 7095% by weight of (A) a copolymer of from 3065% by weight of vinylidene chloride and 7035% by weight of acrylonitrile and (B) 30-5% by weight of a lower N-alkylacrylamide polymer such as poly-N- methacrylamide, polyN-isopropylacrylamide and poly-N-tertiarybutylacrylamide.

The following example illustrates one way in which the cationic compounds of the invention can be used to dye acrylonitrile polymer textile material.

EXAMPLE 153 An amount of 0.1 gram of dye is dissolved by warming in 5 cc. of 2-methoxyethanol. A 2% aqueous solution of a non-ionic surfactant, such as lgepal CA (a polymerized ethylene oxide-alkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture is brought to a volume of 200 cc. with warm water. Five cc. of a 5% aqueous solution of formic acid or acetic acid are added and then 10 grams of fabric made from an acrylic fiber is entered and, in the case of Orlon 42 acrylic textile material, the dyeing is carried out at the boil for one hour. In the case of materials made of Verel modacrylic fiber the dyebath temperature should not exceed C. in order to avoid damage to the fiber. The dyed material is then washed well with water and dried.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as described in the appended claims.

We claim:

1. A compound having the formula wherein is 4-cyano-3-pyrazolyl, 3-pyrazolyl, 4-nitro-3-pyrazolyl, 4-bromo-3-pyrazolyl, 4-ethoxycarbonyl-3-pyrazolyl, 3-isothiazolyl, 5-methylsulfonyl-3-isothiazolyl, 5-nitro- 3-isothiazolyl, 4,5-dimethyl-3-isothiazolyl, 5-cyano-3- isothiazolyl, 2-pyridyl, 4-pyridyl, 2-benzimidaz0lyl, 6-methoxy-2-benzimidazolyl, 6-methylsulfonyl-2-benzimidazolyl or a group having the formula N R a Ra lr l- R is hydrogen, lower alkyl, phenyl, or phenyl substiwherein g tuted with lower alkyl, lower alkoxy, chlorine or R representslower alkylthio, lower alkylthio substibromine; tuted with lower alkoxycarbonyl', lower alkylsulfo- R is lower alkyl or benzyl; nyl, or thiocyanato; 1 n is O or 1; R represents phenyl or phenyl substituted with lower R is phenyl or phenyl substituted with lower alkyL. alkyl; and y lower alkoxy, chlorine, bromine, nitro, or cyano; R represents hydrogen, lower alkyl, phenyl, or B is N; phenyl substituted with lower alkyl. Z is a group having the formula 7. A compound according to claim 6 wherein I n .t

or \n; a

wherein R -is hydrogen, lower alkyl, phenyl, or phenyl R represents methylthio, ethylthio, ethoxycarbonylsubstituted with lower alkyl, lower alkoxy, chlorine or methylthio, or methylsulfonyl; b i and r r 1 R represents phenyl; and

X is an anion. R represents hydrogen. 1 r a 2. A compound according to claim 1 having the for- 8. A compound according to claim 1 having the formula 1 i mula Y 2 S 2 N R N R8 1 R N Y} R JN-N I I R II I I X S 7 i--1\1: NJ

wherein I R represents nitro, chlorine, bromine, cyano, or wherein lower alkylsulfonyl; R represents methyl or ethyl; n R represents phenyl or phenyl substituted w lower R represents phenyl or phenyl substituted with lower alkyl; and alkyl; R represents hydrogen, lower alkyl, phenyl or R represents hydrogen, thiocyanato, lower alkyl, or

phenyl substituted with lower alkyl. alkylsulfonyl; 3. A compound according to claim 2 wherein 40 R represents hydrogen, lower alkyl, phenyl, or R represents 'Q 0f |0W6r alkylsulfonyl; phenyl substituted with lower alkyl, lower alkoxy, R represents phenyl; and chlorine, or bromine; and R represents hydrogen. Z represents 4. A compound according to claim 1 having the formula 2 S N R N\ S I /S /S R L i I 3 R J I wherein R represents nitro, cyano, lower alkylsulfonyl, lower alkoxycarbonyl, or thiocyanato; h i R represents phenyl; and R represents hydrogen, lower alkyl, phenyl or R represents hydrogen or methyl. phenyl substituted with lower alkyl. 5. A compound according to claim 4 wherein 9. A compound according to claim 8 wherein R represents methylsulfonyl, cyano or nitro; R represents methyl; R represents phenyl; and R represents phenyl; R represents hydrogen or methyl. R represents hydrogen or methyl; and

I I R and R represent hydrogen. g compound according to claim 1 having the for 10. A compound according to claim 1 having the formula wherein l R represents methyl or ethyl;

R represents hydrogen, lower alkyl, lower alkoxy,

R represents phenyl or phenyl substituted with lower alkyl; l I p X chlorine or bromine; and Z represents v R wherein R represents methyl or ethyl;

S or R represents phenyl or henyl substituted with lower R alkyl; and

Z represents S I/S wherein R3 or R represents hydrogen, lower alkyl, phenyl or phenyl substituted with lower alkyl.

ll. A compound according to claim 10 wherein wherein R3 represents hydrogen lower alkyl, p y or R represents methyl; phenyl substituted with lower alkyl.

R represents phenyl;

R represents hydrogen or methoxy; and R represents methyl; R represents hydrogen. R represents phenyl; and 12. A compound according to claim 1 having the R represents hydrogen. formula 13. A compound according to claim 12 wherein 

1. A COMPOUND HAVING THE FORMULA
 2. A compound according to claim 1 having the formula
 3. A compound according to claim 2 wherein R4 represents nitro or lower alkylsulfonyl; R2 represents phenyl; and R3 represents hydrogen.
 4. A compound according to claim 1 having the formula
 5. A compound according to claim 4 wherein R5 represents methylsulfonyl, cyano or nitro; R2 represents phenyl; and R3 represents hydrogen or methyl.
 6. A compound according to claim 1 having the formula
 7. A compound according to claim 6 wherein R6 represents methylthio, ethylthio, ethoxycarbonylmethylthio, or methylsulfonyl; R2 represents phenyl; and R3 represents hydrogen.
 8. A compound according to claim 1 having the formula
 9. A compound according to claim 8 wherein R1 represents methyl; R2 represents phenyl; R3 represents hydrogen or methyl; and R7 and R8 represent hydrogen.
 10. A compound according to claim 1 having the formula
 11. A compound according to claim 10 wherein R1 represents methyl; R2 represents phenyl; R9 represents hydrogen or methoxy; and R3 represents hydrogen.
 12. A compound according to claim 1 having the formula
 13. A compound according to claim 12 wherein R1 represents methyl; R2 represents phenyl; and R3 represents hydrogen. 